Functionalized amphiphilic plant-based polymers

ABSTRACT

Amphiphilic copolymers formed from plant oil-derived vinyl ether monomers and polyethylene glycol alkyl vinyl ethers are provided. Nanoparticles coated with these amphiphilic polymers are well-suited for water remediation applications.

CONTINUING APPLICATION DATA

This application is a continuation of international application PCT/US2013/041621, filed May 17, 2013, and a continuation-in-part of U.S. application Ser. No. 13/896,874, filed May 17, 2013, each of which claims the benefit of U.S. Provisional Application Ser. No. 61/649,016, filed May 18, 2012, each which is incorporated by reference herein in its entirety.

GOVERNMENT FUNDING

This invention was made with government support under Grant No. CMMI-1125674, awarded by the National Science Foundation. The government has certain rights in the invention.

BACKGROUND

Nanoscale structures such as nanoparticles and nanotubes have unique physiochemical properties. Their extremely high surface area, for example, provides many advantages over conventional particles with dimensions in the micron scale. Carbon nanotubes additionally exhibit extraordinary thermal conductivity and unique mechanical and electrical properties.

Because of their unique properties, nanoscale structures have many diverse uses. For example, metal nanoparticles are attractive for environmental remediation of various contaminants. Various chlorinated aliphatic hydrocarbons and toxic metals can be remediated using metal nanoparticles such as zero valent iron (Fe⁰) nanoparticles (known as FeNP or nZVI—nanoscale zero valent iron). Metal nanoparticles have also been used for the remediation of groundwater contaminated with chemicals used in explosives. The effectiveness of a remediation approach depends on various factors, one of which is the ability to access the contaminant(s) with the metal nanoparticles. Fe⁰ nanoparticles, for example, are highly reactive and react rapidly with surrounding media in the subsurface (dissolved oxygen and/or water, for example). Thus, significant loss of reactivity can occur before the particles are able to reach the target contaminant.

For effective bioremediation and a variety of applications, it is necessary to individually disperse and suspend the nanoparticles in a liquid medium. One of the most important liquid mediums is water since it is inexpensive and non-toxic. Due to the high density of many nanoparticles and strong interparticle surface interactions, suspension of nanoparticles in water is challenging. Metal nanoparticles, such as Fe⁰ nanoparticles, tend to flocculate or aggregate when added to water due to interparticle van der Waal interactions. Flocculation and aggregation reduce the effective surface area of the metal and cause precipitation or sedimentation of the metal from the aqueous phase.

WO2009/111722 (Bezbaruah et al., published 11 Sep. 2009) describes metal nanoparticles entrapped in or surface-modified with an amphiphilic polysiloxane graft copolymer (APGC). The resultant nanoparticle exhibits increased colloidal stability, reduced oxidation by non-target compounds, and affinity toward water/contaminant interfaces. However, the copolymer is not sufficiently biodegradable to render the nanoparticle delivery vehicles described therein suitable for all environmental applications.

SUMMARY OF THE INVENTION

The present invention provides functionalized amphiphilic plant-based polymers having utility in a wide variety of settings including commercial, industrial, environmental, medical, and veterinary applications. The polymers of the invention can be used, for example, as dispersal and suspension agents, for environmental remediation, as solubilizers, detergents, paper coatings, pigment dispersants, fabric treatments, delivery of therapeutic agents, personal-care products, and the like.

In one aspect, the invention provides compounds, composites, aggregates, compositions, delivery vehicles, systems, and methods for dispersing and suspending nanoscale and micron scale structures, preferably metal nanoparticles and carbon nanotubes, more preferably zero-valent iron (Fe⁰) nanoparticles (FeNPs) in aqueous environments. Methods of making and using said compounds, composites, aggregates, compositions, delivery vehicles, and systems are also provided.

The copolymer compounds of the invention can be used to facilitate improved dispersion and suspension of FeNPs in water for application in ground water remediation. The novel compositions effectively inhibit sedimentation of FeNPs from water. For example, copolymer compounds of the invention can be used to protect, disperse and suspend FeNPs in decontamination efforts involving chlorinated hydrocarbons, such as trichloroethylene. The copolymers described herein are not only high effective with respect to suspending nanoparticles in water but also exhibit high biodegradability. Biodegradability is important for environmental applications because the polymer is typically not recovered after treatment of a ground water contaminant plume. In addition, compared to other approaches, this copolymer technology enables compositions to be highly tailored or optimized for a given nanoparticle and application.

In another aspect, the copolymers of the invention can be used to deliver inorganic remediation agents and organic or bioremediation agents. Bioremediation agents include microorganisms or microorganism cultures, enzymes, enzyme additives, nutrients, nutrient additives, and the like that significantly increase the rate of biodegradation to mitigate the effects of the contaminant.

The copolymers of the invention are amphiphilic and thus are also useful in detergent compositions. Advantageously, the amphiphilic copolymers of the invention are expected to prevent re-deposition of dirt particles onto fabrics. Re-deposition can occur because the particles are dense and can participate in electrostatic interactions with fibers. However, these interactions may be reduced or prevented by the chelating action of the amphiphilic copolymers which effectively suspend the particles in an aqueous environment. Additionally, the amphiphilic copolymers, because they have numerous chelation sites, are expected to coordinate metal ions present in water and inhibit precipitation of metal-associated complexes.

Because they are biodegradable and non-toxic, they find additional utility as a means for solubilizing, dispersing and/or suspending therapeutic or diagnostic agents in medical or veterinary applications, and as vehicles for drug delivery.

The copolymers can effectively suspend carbon nanotubes in water. In addition, due to unsaturation in the vinyl ether [e.g., 2-(vinyloxy)ethyl soyate] repeat units, the aqueous suspensions of carbon nanotubes can be combined with a catalyst package for auto-oxidation cure to produce cured coatings containing dispersed carbon nanotubes. Further, the copolymers of the invention are surface active due to their amphiphilic nature. In addition, it is known that carboxylic acid groups can be used to chelate metal ions in water. Thus, the compounds of the invention may provide antimicrobial activity, for example, via a cell wall disruption mechanism, and can find utility as disinfectants. The compounds of the invention may also be useful for removing microbial biofilms.

Other applications include the use of the copolymers to suspend nanostructures in inks, including conductive inks. Paper coatings represent another useful application, because paper contains calcium carbonate and cellulose fibers, both of which have an affinity for carboxylic groups. Paper coatings are designed to impart some hydrophobicity to a highly hydrophilic structure. The fatty acid chains will provide hydrophobicity as well as the potential for crosslinking via auto-oxidation. Further, as noted, the polymers are biodegradable.

An exemplary polymer is a copolymer that includes two or more repeat units, including at least a first monomer which is derived from a plant-derived, preferably a plant oil-derived vinyl ether monomer, such as 2-(vinyloxy)ethyl soyate (2-VOES), and at least a second monomer which is a polyalkylene glycol alkyl vinyl ether, preferably a polyethylene glycol alkyl vinyl ether, such as triethylene glycol ethyl vinyl ether (TEGEVE) or triethylene glycol methyl vinyl ether (TEGMVE). Additional monomeric units (e.g., a third monomer, fourth monomer, etc.) may be included as desired for the particular application.

In a preferred embodiment, the copolymer contains at least one functional group, such as a carboxylic acid group, that is capable of chelating or coordinating to a metal ion or atom. Alternatively or additionally, other functional groups that can be incorporated into the amphiphilic copolymer for chelating or coordinating to a metal ion or atom include a silane, such as an alkoxysilane group, amine, thiol, —N(CH₂CO₂H)₂ (analogous to the chelating group used in ethylenediaminetetraacetic acid, EDTA), phosphonate, phosphonic acid, sulfonate, sulfonic acid, anhydride, and substituted phenol (preferably a 1- or 2-substituted phenol).

In one embodiment, the functional group is grafted onto one or more of the repeat units derived from the plant-oil derived vinyl ether monomer (e.g., the 2-VOES).

In another embodiment, the copolymer optionally includes a third monomer, and the functional group is incorporated into the polymer as part of an optional third monomer. The optional third monomer is preferably a monomer with an electron-poor double bond, more preferably maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid. When maleic anhydride or citraconic anhydride (followed by hydrolysis), or fumaric acid is incorporated into the polymer backbone, the functional group (e.g., the carboxylic acid) is positioned on the polymer backbone.

Exemplary plant oil-derived vinyl ether monomers useful as a repeat unit of the copolymer are described in WO2011/060293 (Chisholm et al.), published May 19, 2011. An exemplary plant-oil derived monomer has the structure

wherein R¹ is a divalent organic group that functions as a spacer between the vinyl ether and the heteroatom; Z is a heteroatom selected from O, N or S; R² contains an aliphatic group, preferably derived from a renewable resource such as a plant or plant oil; and R⁶, R⁷, and R⁸ are each independently H or alkyl. The plant oil is preferably a vegetable or nut oil, more preferably soybean oil. Use of a plant oil-derived polymer as a component of the copolymer backbone advantageously increases the biodegradability and biocompatibility of the copolymer, opening up many new environmental, industrial and medical/veterinary applications.

The fatty acid pendant group of the vinyl ether monomer can be derived directly or indirectly from a plant oil. For example, the vinyl ether compound can based on a plant oil-derived compound such as a transesterified plant oil-based long chain alkyl ester, such as a biodiesel compound, for example an alkyl soyate such as methyl soyate.

In some embodiments, the copolymer of the invention contains a plurality of plant oil derived monomers, such that for each of the plurality of monomers, R² is independently an aliphatic group derived from a renewable resource such as a plant oil, preferably a C8-C21 aliphatic group derived from a plant oil.

An exemplary polyethylene glycol alkyl vinyl ether useful as a component of the copolymer has the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl, preferably methyl or ethyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20. The plant oil is preferably a vegetable or nut oil, more preferably soybean oil

Exemplary functional groups which can chelate or coordinate to a metal ion or atom include, for example, carboxylic acid and phosphonate. The resulting copolymer is an amphiphilic copolymer and has coordinating groups that allow it to suspend nanoparticles or carbon nanotubes. The chelating or coordinating groups, in conjunction with the aliphatic region of the plant-oil-based vinyl ether component of the copolymer, allow for efficient adsorption of copolymer molecules onto the surface of the FeNP while the water-soluble polyethylene glycol copolymer components allow for dispersibility and colloidal stability in an aqueous medium. The hydrophobicity of the plant oil fatty acid chain causes the copolymer to have a high affinity for the water/contaminant interface, and also allows permeation of non-polar or hydrophobic contaminants through the copolymer covering to the FeNP surface.

Also provided are polymer-treated micron scale and nanoscale structures, such as nanoparticles and nanotubes, which are coated with, surface-modified or dispersed within the copolymer of the invention. Compositions that include the copolymers are also provided, as well as compositions that include the coated micron scale and nanoscale structures. Methods of making and using the coated structures are also provided.

As used herein, the term “polymer” is inclusive of homopolymer and copolymer. The term “copolymer” is inclusive of a polymer containing two or more different monomers, including three different monomers (e.g., a terpolymer), four different monomers, and so on.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows sedimentation behavior of zerovalent iron nanoparticles (NZVIs) treated with various carboxylic acid-functional copolymers.

FIG. 2 shows sedimentation behavior of NZVIs comparing bare NZVIs to NZVIs treated with copolymer5 and copolymer5-C, respectively.

FIG. 3 shows images of dispersions of bare NZVIs in deoxygenated DI water and CNZVIs treated with copolymer5-C in deoxygenated DI water at different times after shaking.

FIG. 4 shows images of dispersions of multiwall carbon nanotubes (MCNTs) in water with (CMCNT) and without (MCNT) treatment with copolymer5-C. Images were taken two hours after preparation.

FIG. 5 shows biological oxygen demand (BOD) values as a function of time using respirometric experiments. The graph shows the BOD of soybean oil, VOES-TEGEVE copolymers, and VOES-TEGEVE copolymers coated NZVIs over time.

FIG. 6 shows growth of microorganisms in the presence of soybean oil, VOES-TEGEVE copolymers, and VOES-TEGEVE copolymers coated NZVIs.

FIG. 7 shows, as the left panel, functionalization of the aliphatic side chain of a polymer and, as the right panel, the incorporation of the monomer maleic anhydride into the polymer backbone resulting in the functional group (e.g., the carboxylic acid) being directly attached to the polymer backbone.

FIG. 8 shows functionalization of a copolymer by grafting carboxylic acid onto a plant oil-based component using mercaptopropionic acid, a carboxylated thiol.

FIG. 9 shows a representative copolymerization reaction.

FIG. 10 shows functionalization of the copolymer shown in FIG. 9.

FIG. 11 further describes a component, R¹⁸, of the functionalized copolymer of FIG. 10.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The copolymer of the invention includes, as first and second repeat units, at least one plant-derived vinyl ether monomer component, preferably a plant oil-derived vinyl ether monomer, and at least one polyalkylene glycol alkyl vinyl ether component. Optionally, the copolymer contains one or more additional monomer components. Preferably and advantageously, the copolymer contains a functional group capable of chelating or coordinating to a metal ion or atom.

An illustrative plant oil-derived vinyl ether monomer is vinyl ether of soybean oil fatty acid esters (VESFA), also referred to herein interchangeably as 2-(vinyloxy)ethyl soyate (2-VOES), although it should be understood that the monomer is not limited to a monomer produced from soybean oil. As noted elsewhere herein, any plant oil can be used, for example corn oil. The various methods and uses described herein, therefore, although described for convenience with reference to monomer derived from soybean oil, apply generally to embodiments derived from any suitable plant oil. VESFA is derived from the transesterification of soybean oil (the exemplary plant oil) with ethylene glycol monovinylether. Because soybean oil contains five different fatty acids (stearic acid, oleic acid, linoleic acid, palmitic and linolenic acid) the vinylether monomers produced by transesterification of soybean oil include a mixture of vinylethers of stearic acid, oleic acid, linoleic acid, palmitic acid and linolenic acid esters.

Plant oils that can be used to form the vinyl ether monomer component of the copolymer include vegetable oils, such soybean oil, linseed oil, tung oil, oiticica oil, perilla oil, safflower oil, sunflower oil, castor oil, cotton seed oil, flax seed oil, grape seed oil, high oleic soybean oil, palm oil, palm kernel oil, olive oil, canola oil, rapeseed oil, and corn oil; oil from trees or wood pulp such as tall oil and palm oil, or nut-based oils such as cashew oil and peanut oil. Vegetable oils typically include at least one triglyceride and contain esters from fatty acids such, for example, oleic acid, stearic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, myristic acid, arachidic acid, and palmitioleic acid. It should be understood, however, that plant-derived vinyl ether monomers can be formed not just from plant triglycerides, but also from aliphatic plant compounds of any type, including individual isolated, purified and/or derivatized plant-derived fatty acid molecules.

Vinyl ether monomers that are useful as components of the copolymer of the invention include vinyl ethers of plant oil-derived fatty acids, more particularly, vinylethers of soybean oil-derived fatty acids (VESFA). A preferred monomer has the structure R⁶R⁷C═C(R⁸)—O—R¹—Z—C(O)—R², wherein R¹ is divalent organic group that functions as a spacer between the vinyl ether and the heteroatom; Z is a heteroatom selected from O, N or S; R² contains an aliphatic group derived from a renewable resource such as a plant oil, such as soybean oil; and R⁶, R⁷, and R⁸ are each independently H or alkyl.

A particularly preferred monomer has the structure CH₂═CH—O—R¹—Z—C(O)—R².

The spacer, R¹, can be a branched or unbranched hydrocarbon having 1 to 40 or more carbon atoms; it may be substituted or unsubstituted at one or more sites; it may be saturated or unsaturated at one or more sites; it may contain one or more monocyclic or polycyclic divalent ring structures (aliphatic or aromatic); and it may contain one or more divalent functionalities such as ether, thioether, ester, thioester, amine and amido.

In one embodiment, the spacer R¹ is (CR³R⁴)_(m) wherein, for each instance of m, each of R³ and R⁴ is independently selected from H, methyl, ethyl, propyl, hydroxy, methyl, methoxy, aryl, and halo, including substituted forms thereof; and wherein m is 1 to 10, more preferably m=1, 2, 3, 4 or 5.

In another embodiment, the spacer R¹ is (CR³R⁴)_(n)—X—(CR³R⁴)_(p) wherein n and p are each independently 0, 1, 2, 3, 4 or 5; X is O (ether), C(O) (carbonyl), OC(O) (ester), C(O)O (ester), S (thioether), OS(O) (thioester), S(O)O (thioester), N(R⁵) (a secondary tertiary amine, wherein R⁵ is H or an organic substituent), N(H)C(O) (amide) C(O)N(H) (amide), or a substituted unsubstituted monocyclic or polycyclic cycloaliphatic or aromatic moiety, preferably cyclohexyl or benzyl; and R³ and R⁴ are independently selected from H, methyl, ethyl, propyl, hydroxy, methyl, methoxy, aryl, and halo, including substituted forms thereof. Monomers having a spacer (R′) that contains a cycloaliphatic moiety may be expected to be more rigid, which may increase the glass transition temperature of a polymer into which it is incorporated, a property that would be desirable for many applications.

R² is any aliphatic moiety obtained from a plant, preferably a plant oil. R² is preferably a C8-C21 aliphatic group, more preferably a C8-C21 alkyl group or a C8-C21 alkenyl group, even more preferably a linear C8-C21 alkyl group or a linear C8-C21 alkenyl group. The aliphatic group preferably includes a linear chain of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms, and preferably contains 0 (saturated), 1 (monounsaturated), 2 or 3 double bonds. Preferred polymers, co-polymers, and polymeric materials are those derived from a preferred monomer.

The plant oil-derived vinyl ether monomer may contain an ester linkage (in embodiments where Z═O), an amide linkage (in embodiments where Z═N) or a thioester linkage (in embodiments where Z═S). Embodiments having an amide linkage may be expected to exhibit certain advantages with respect to thermal and mechanical properties due to the introduction of hydrogen bonding via the amide nitrogen.

Exemplary vinyl ether monomers, wherein R² is derived from a plant oil, are shown below.

Additional exemplary vinyl ether monomers and methods of making them are described in WO2011/060293 (Chisholm et al.).

As used herein, the terms “aliphatic” or “aliphatic group” mean a saturated or unsaturated linear (i.e., straight chain), cyclic, or branched hydrocarbon group. The hydrocarbon or hydrocarbon group can be substituted or unsubstituted. The term “aliphatic” encompasses monovalent and divalent aliphatic groups, including alkyl (e.g., —CH₃) (or alkylene if within a chain such as —CH₂—), alkenyl (or alkenylene if within a chain), and alkynyl (or alkynylene if within a chain) groups, as well as substituted forms thereof, for example.

The terms “alkyl” or “alkyl group” mean a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, amyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like, as well as their divalent counterparts. “Alkyl” and “alkylene” are also meant to include substituted alkyls and alkylenes. Suitable substituents include aryl groups (which may themselves be substituted), as in the case where the “alkyl” is a phenyl-substituted methyl group (e.g., a benzyl moiety). Other suitable substituents include heterocyclic rings (saturated or unsaturated and optionally substituted), hydroxy groups, alkoxy groups (which is meant to include aryloxy groups (e.g., phenoxy groups)), thiol groups, alkylthio groups, arylthio groups, amine groups (which is meant to include unsubstituted, monosubstituted, or disubstituted (e.g., with aryl or alkyl groups) amine groups), carboxylic acid groups (which is meant to include COOH groups as well as carboxylic acid derivatives, e.g., carboxylic acid esters, amides, etc.), phosphine groups, sulfonic acid groups, halogen atoms (e.g., F, Cl, Br, and I), and the like. Further, alkyl groups bearing one or more alkenyl or alkynyl substituents (e.g., a methyl group itself substituted with a prop-1-en-1-yl group to produce a but-2-en-1-yl substituent or a methyl group itself substituted with a vinyl group to produce an allyl substituent) are meant to be included in the meaning of“alkyl.”

The terms “alkenyl” or “alkenyl group: mean an unsaturated, linear or branched monovalent or divalent hydrocarbon group with one or more olefinically unsaturated groups (i.e., carbon-carbon double bonds), such as a vinyl group. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like.

The term “alkynyl group” means an unsaturated, linear or branched monovalent or divalent hydrocarbon group with one or more carbon-carbon triple bonds. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term “aliphatic” also encompasses monovalent or divalent cyclic hydrocarbons such as cycloaliphatic groups or heterocyclic groups. The term “cycloaliphatic” refers to a cyclic or polycyclic hydrocarbon group, which may have properties resembling those of linear aliphatic groups. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. The term “cycloaliphatic” also includes aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. The term “heterocyclic group” means a cyclic or polycyclic closed ring hydrocarbon in which one or more of the atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.).

Unless otherwise specified, an aliphatic group can contain 1 or 2 or 3 or 4, and so on, up to 38 or 39 or 40 carbon atoms; that is, 1 to 40 carbon atoms. In certain embodiments, aliphatic groups contain 1 to 20 carbon atoms. In certain embodiments, aliphatic groups contain 2 to 20 carbon atoms. In certain embodiments, aliphatic groups contain 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbons atoms. Exemplary aliphatic groups include, but are not limited to, linear or branched alkyl, alkylene, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “unsaturated”, as used herein, means that a moiety has one or more double or triple bonds.

An aliphatic group may be unsubstituted, or optionally substituted with one or more substituents. “Substituted” means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds. The term “stable”, as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

Suitable substituents include, but are not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aroyl, halo (e.g., F, Cl, Br and I), hydroxy, oxo, nitro, alkoxy, amino, amido, imino, azido, mercapto, acyl, carbamoyl, carboxy, carboxamido, amidino, guanidino, thiol, alkylthiol, arylthio, sulfonyl, sulfinyl, sulfonamido, phosphine, formyl, cyano, and ureido groups.

The term “alkoxy”, as used herein refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.

The term “acyl”, as used herein, refers to a carbonyl-containing functionality, e.g., —C(═O)R′, wherein R′ is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is a substituted (e.g., with hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g., forming a carboxylic acid, ester, or amide functionality). The term “acyloxy”, as used here, refers to an acyl group attached to the parent molecule through an oxygen atom.

The terms “aromatic,” “aromatic group,” “aryl” and “aryl group” mean a mono- or polynuclear aromatic hydrocarbon group. These hydrocarbon groups may be substituted with heteroatoms, which can be in the form of functional groups. The term “aromatic” or “aryl” used alone or as part of a larger moiety as in “aromatic hydrocarbon,” “aralkyl,” “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term “aryl” may be used interchangeably with the term “aryl ring” or “aromatic ring.” In certain embodiments of the present invention, “aryl” refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents. Also included within the scope of the term “aryl”, as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.

In describing substituents, the term “radical” is sometimes used. In this context, “radical” means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent.

The term “heteroatom” means an element other than carbon (e.g., nitrogen, oxygen, sulfur, chlorine, etc.). A “hetero-” moiety as described herein, such as a heteroaliphatic group, a heterocyclic group and the like, refers to a moiety having, in place of one or more carbon atoms, a heteroatom independently selected from nitrogen, oxygen, or sulfur. Examples of saturated or partially unsaturated heterocyclic groups include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”, “heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and “heterocyclic radical”, are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. The term “heterocyclylalkyl” refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.

Preferably, the vinyl ether monomer component of the copolymer of the invention is derived from a plant product, particularly a plant product that contains a fatty acid chain, more preferably vegetable or a nut oil. In on embodiment, the vinyl ether monomer is derived from one of the plant fatty acids found in soybeans: stearic acid, oleic acid, palmitic, linoleic acid or linolenic acid. The fatty acid pendant group of the vinyl ether monomer can be derived directly or indirectly from a plant oil. For example, the vinyl ether compound can be derived from a plant oil-derived compound such as a transesterified plant oil-based long chain alkyl ester, such as a biodiesel compound, for example an alkyl soyate such as methyl soyate.

In one embodiment, plant-oil derived vinyl ether monomers are synthesized using base-catalyzed transesterification of a plant oil, such as soybean oil, with ethylene glycol vinyl ether, propylene glycol vinyl ether, isopropylene glycol vinyl ether, butylene glycol vinyl either or iso-butylene ether, which compounds are also known as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, isopropylene glycol monovinyl ether, butylene glycol monovinyl ether and iso-butylene glycol monovinyl ether. The base can be potassium hydroxide, sodium hydroxide, or any convenient base. Ethylene glycol vinyl ether and butylene glycol vinyl ether are relatively inexpensive chemicals, and the resulting monomers are isolated in high purity. In another embodiment, the monomer is synthesized using acid-catalyzed transesterification. More generally, any convenient transesterification method can be used to generate the vinyl ether plant oil-derived fatty acid ester monomers of the invention.

Vinyl ethers can also be synthesized from fatty alcohols. The plant-derived vinylether monomer component of the copolymer of the invention can include one or more monomers derived from fatty alcohol based vinyl ethers. The inclusion of fatty alcohol-derived vinyl ether monomers provides hydrolytic stability to the copolymer, especially if used in a water-based system that is acidic or basic. Fatty alcohols are typically produced from hydrogenation of fatty acids. The conversion of the fatty alcohols to the vinyl ether can be accomplished using vinylation with acetylene, a process involving several steps.

WO2011/060293 (Chisholm et al.) describes the production of a plant oil-derived vinyl ether directly from a reaction between a vinyl ether possessing a nucleophilic group and the plant oil, preferably vegetable oil, by a single-step simple nucleophilic substitution reaction similar to the process used to produce biodiesel (i.e. methyl esters of vegetable oil fatty acids). The resulting monomer is much easier and less expensive to make.

An illustrative polyethylene glycol alkyl vinyl ether component of the copolymer has the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl, preferably methyl or ethyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20.

The spacer, R¹², can be a branched or unbranched hydrocarbon having 1 to 40 or more carbon atoms; it may be substituted or unsubstituted at one or more sites; it may be saturated or unsaturated at one or more sites; it may contain one or more monocyclic or polycyclic divalent ring structures (aliphatic or aromatic); and it may contain one or more divalent functionalities such as ether, thioether, ester, thioester, amine and amido.

In one embodiment, the spacer R¹² is (CR³R⁴)_(m) wherein, for each instance of m, each of R³ and R⁴ is independently selected from H, methyl, ethyl, propyl, hydroxy, methyl, methoxy, aryl, and halo, including substituted forms thereof; and wherein m is 1 to 10, more preferably m=1, 2, 3, 4 or 5.

In another embodiment, the spacer R¹² is (CR³R⁴)_(n)—X—(CR³R⁴)_(p) wherein n and p are each independently 0, 1, 2, 3, 4 or 5; X is O (ether), C(O) (carbonyl), OC(O) (ester), C(O)O (ester), S (thioether), OS(O) (thioester), S(O)O (thioester), N(R⁵) (a secondary tertiary amine, wherein R⁵ is H or an organic substituent), N(H)C(O) (amide) C(O)N(H) (amide), or a substituted unsubstituted monocyclic or polycyclic cycloaliphatic or aromatic moiety, preferably cyclohexyl or benzyl; and R³ and R⁴ are independently selected from H, methyl, ethyl, propyl, hydroxy, methyl, methoxy, aryl, and halo, including substituted forms thereof. Monomers having a spacer (R¹²) that contains a cycloaliphatic moiety may be expected to be more rigid, which may increase the glass transition temperature of a polymer into which it is incorporated, a property that may be desirable for some applications.

A particularly preferred polyethylene glycol alkyl vinyl ether component of the copolymer is triethylene glycol ethyl vinyl ether (TEGEVE), which has the structure

A copolymer of the invention is formed from at least one plant oil-derived vinyl ether monomer and at least one polyethylene glycol alkyl vinyl ether.

The copolymer optionally includes one or more additional monomers, such as monovinylidene monomers. In one embodiment, the copolymer optionally includes a third monomer. The optional third monomer preferably contains an electron-poor double bond, such as maleic anhydride. An example of an electron-poor double bond is a disubstituted double bond in which at least one substituent at each carbon of the double bond has a carbonyl group. The double bond of the vinyl ether is electron-rich due to the oxygen atom next to the double bond; while the double bond of maleic anhydride is electron-poor due to the two carbonyl groups attached to the double bond. Assuming the electron-donor/electron-acceptor monomer pair behaves as a single entity during free radical polymerization, it is expected that the other vinyl-functional monomers that readily free-radically polymerize could be copolymerized with the electron-donor/electon-acceptor pair to produce terpolymers or copolymers with more than three different repeat units. Monomers that readily undergo free-radical polymerization include the important industrially relevant monomers such as methyl methyacrylate, methyl acrylate, n-butyl methacrylate, n-butyl acrylate, styrene, ethyl methacrylate, ethyl acrylate, vinyl acetate, t-butyl acrylate, t-butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.

Exemplary compounds that can be optionally incorporated into the copolymer as a monomer that contains an electron-poor double bond include:

Advantageously, the functional group that chelates or coordinates the metal atom can be incorporated into the polymer as part of an optional third monomer. More specifically, the incorporation of the monomer maleic anhydride or citraconic anhydride (followed by hydrolysis), or the monomer fumaric acid, into the polymer backbone results in the functional group (e.g., the carboxylic acid) being directly attached to the polymer backbone, as shown in FIG. 7.

The copolymer can be a random copolymer, a block copolymer, a star polymer, a telechelic polymer, or a graft copolymer. It may or may not be cross-linked. A preferred copolymer is one that is characterized by a repeating structure as shown below:

wherein the R groups, Z and n are as defined above for the component monomers; and wherein x is 2 to 500 and y is 2 to 500.

Chemical derivatives of the copolymer, including but not limited to an epoxy-functional copolymer, an acrylate-functional copolymer and a polyol copolymer, are also encompassed by the invention. An epoxy-functional copolymer includes at least one aliphatic group derived from a plant oil that has been functionalized to include at least one epoxide group; an acrylate functional copolymer includes at least one aliphatic group derived from a plant oil that has been functionalized to include at least one acrylate-functional group; and a polyol copolymer includes at least one aliphatic group derived from a plant oil that has been functionalized to include at least one alcohol group. The aliphatic group at R² thus optionally comprises an epoxide group, an acrylate-functional group, a vinyl group, an alcohol group, or other reactive of functional group.

Additionally or alternatively, the copolymer is optionally activated or functionalized with one or more activating or functional groups capable of chelating or coordinating to a metal ion or atom. In a preferred embodiment, the R² group(s) are functionalized or activated at the site of one or more double bonds in the plant oil-derived aliphatic chain. The double bonds present in the aliphatic chain may be internal (divalent) or may be terminal. Activation or functionalization can occur either before, during or after the copolymerization reaction. Preferably, the attachment of the chelating/coordinating groups occurs after copolymerization. These functional groups typically include oxygen, sulfur, silicon or nitrogen atoms and include, for example, carboxylic acid and phosphonate, as well silane, such as an alkoxysilane group, amine, thiol, —N(CH₂CO₂H)₂ (analogous to the chelating group used in ethylenediaminetetraacetic acid, EDTA), phosphonate, phosphonic acid, sulfonate, sulfonic acid, anhydride, and substituted phenol (preferably a 1- or 2-substituted phenol). The functional groups attached to the copolymer can contain single or multiple coordinating/chelating groups. For example, the copolymer can be activated or functionalized with an ethylenediaminetetraacetic acid (EDTA) or derivative thereof, as described below, which imparts between 2 and 4 carboxylic acids per reactive site on the copolymer.

The copolymer preferably may contain a plurality of different plant oil-derived vinyl ether monomers, in that R² can encompass a plurality of aliphatic groups R_(n) where n=1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The aliphatic groups are optionally activated or functionalized. For example, when the monomers are derived from an oil such as soybean oil that contains esters derived from five fatty acids, the copolymer may contain plant oil-derived vinyl ether monomers having five different aliphatic groups, e.g., R₁=stearate, R₂=oleate, R₃=linoleate, R₄=linoleate and R₅=linolenate. It should be understood that the five monomers are typically randomly dispersed throughout the polymer, according to their abundance. An exemplary composition of soybean oil is about 11% palmitic acid, about 4% stearic acid, about 23% oleic acid, about 54% linoleic acid, and about 7% linolenic acid.

An exemplary copolymerization reaction between 2-(vinyloxy)ethyl soyate (2-VOES) and triethylene glycol ethyl vinyl ether (TEGEVE) is shown below:

where x and y are independently 2 to 500. As shown in FIG. 8, the resulting copolymer can be functionalized by grafting carboxylic acid onto the plant oil-based component, for example by using a carboxylated thiol, in this case mercaptopropionic acid.

The copolymerization reaction can be shown more generally as in FIG. 9, wherein the R groups, Z, n, x, and y, are as defined above.

Functionalization of the resulting copolymer can be accomplished, for example, by reacting it with a functionalized thiol, as shown in FIG. 10, wherein R¹ through R¹³, Z, n, x and y are as defined above; R is C or Si; R¹⁴ is optional and, if present, is a spacer as defined elsewhere herein, preferably an alkyl, at least one of R¹⁵, R¹⁶, and R¹⁷ includes at least one functional group, such as, but not limited to, carboxyl, phosphonate, silane (e.g., an alkoxysilane group), amine, thiol, —N(CH₂CO₂H)₂ (analogous to the chelating group used in ethylenedi ami netetraacetic acid, EDTA), phosphonate, phosphonic acid, sulfonate, sulfonic acid, anhydride, and substituted phenol (preferably a 1- or 2-substituted phenol), which functional group is capable of chelating or coordinating to a metal ion or atom; the other(s) of R¹⁵, R¹⁶, and R¹⁷ are each independently H or alkyl; and wherein R¹⁸ contains the reaction product as shown in FIG. 11.

The invention is not limited by the chemistry used to attach the functional group to the co-polymer. The chemistry exemplified herein involves the use of a thiol-ene reaction to attach the functional group (in this case, a carboxylic acid) directly. Alternatively, a thiol such as 2-mercaptoethylamine can be reacted with the plant oil-derived polymer chain to yield a primary amine, which can in turn be reacted with, for example, two equivalents of a haloacetic acid to produce a doubly derivatized compound. Many other chemistries are known that can make use of the reactive double bond(s) in the plant-oil derived chain as attachment sites for the chelating/coordinating group(s). For example, the double bonds can be epoxidized, then reacted with a dicarboxylic acid in the presence of a base catalyst in ring opening reaction that covalently attaches the dicarboxylic acid, leaving one of the carboxylic acids free and available for chelating or coordinating. Cross-linking can be controlled or avoided by providing the dicarboxylic acid in excess. Many different carboxylic acids are commercially available for use as reactants. Other chemistries allow attachment of a chelating/coordinating agent to an acrylated plant-oil derived chain, for example via a Michael addition reaction.

In another embodiment, the copolymer optionally includes a third monomer, and the functional group is incorporated into the polymer as part of an optional third monomer. The optional third monomer preferably contains an electron-poor double bond; more preferably maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid. When maleic anhydride or citraconic anhydride (followed by hydrolysis), or fumaric acid is incorporated into the polymer backbone, the functional group (e.g., the carboxylic acid) is attached directly to the polymer backbone.

Copolymerization reactions can be accomplished using any suitable copolymerization technique. For example, carbocationic polymerization or free radical polymerization can be used. Exemplary copolymerizations are described in the following examples.

Also provided by the invention are coated materials and structures such as small particles and tubes. The coated materials are coated with a copolymer of the invention in order to prevent flocculation, aggregation, sedimentation and/or precipitation, and optionally to enhance affinity for a water/contaminant interface. In some embodiments, the copolymer coating is permeable so as to allow contact of a targeted substance, such as a contaminant, with the micron scale or nanoscale particle or tube, such as a nanoparticle having activity as a remediation agent. The coated materials can be micron scale or nanoscale. In one embodiment, the coated material is a nanoparticle, preferably a metal nanoparticle, more preferably an iron nanoparticle, such as a zero valent iron nanoparticle (FeNP). Other nanoparticles, such as metal oxides, carbon black, and graphene, are also contemplated. The coated nanoparticle may, additionally or alternatively, contain other metals, such as zinc, magnesium, palladium or nickel. In another embodiment, the coated structure is a nanotube, preferably a carbon nanotube. When formulated for use in water remediation, such as groundwater remediation or clearing contaminants from open water such as lakes, rivers, streams or oceans, the coated material can be a water remediation agent such as an inorganic, organic, or bioremediation agent. Bioremediation agents include but are not limited to microorganisms or microorganism cultures, enzymes, enzyme additives, nutrients, nutrient additives, and the like that significantly increase the rate of biodegradation to mitigate the effects of the contaminant. Contaminants that can be targeted with the remediation agent delivery system of the invention include but are not limited to chromate, arsenic, technetium, uranium, chlorine, nitrate, pesticides, viruses, oil, and petroleum.

Accordingly, in exemplary embodiments, the invention provides copolymers, composition, articles and the like that can contain any of the following features in any combination. The invention thus includes a copolymer comprising:

at least one first monomer comprising a plant-derived vinyl ether monomer having the structure

wherein R¹ is a divalent organic group; Z is a heteroatom selected from O, N or S; R² comprises an aliphatic group derived from a plant; and R⁶, R⁷, and R⁸ are each independently H or alkyl;

and at least one second monomer comprising a polyethylene glycol alkyl vinyl ether having the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20.

The first monomer can be derived from a plant oil.

The oil-derived monomer may comprise a plurality of monomers, and for each of the plurality of monomers, R² can be independently a C8-C21 aliphatic group derived from a plant oil.

The aliphatic group can comprise at least one functional group selected from the group consisting of an epoxide group, an acrylate-functional group, a vinyl group, and an alcohol group.

The copolymer can further comprise at least one functional group comprising a chelating or coordinating group.

The aliphatic group can comprise the at least one functional group comprising a chelating or coordinating group.

The copolymer can further comprise at least one third monomer comprising an electron-poor double bond.

The third monomer can comprise maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid.

The chelating or coordinating group can be directly attached to the polymer backbone.

The invention further includes a copolymer comprising a repeating structure comprising:

wherein R¹ is a divalent organic group; Z is a heteroatom selected from O, N or S; R² comprises an aliphatic group derived from a plant; and R⁶, R⁷, and R⁸ are each independently H or alkyl; R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; n is 2 to 20; and x and y are independently 2 to 500.

The polymer can comprise a plurality of plant oil-derived monomers, wherein for each of the plurality of monomers, R² is independently a C8-C21 aliphatic group derived from a plant oil

The aliphatic group can comprise at least one functional group selected from the group consisting of an epoxide group, an acrylate-functional group, a vinyl group, and an alcohol group.

The copolymer can further comprise at least one functional group comprising a chelating or coordinating group.

The aliphatic group can comprise the at least one functional group comprising a chelating or coordinating group.

The copolymer can further comprise at least one additional monomer comprising an electron-poor double bond.

The additional monomer can comprise maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid.

The chelating or coordinating group can be directly attached to the polymer backbone.

The invention further provides a composition comprising any of the described copolymers.

The composition may further comprise bioremediation agent.

The bioremediation agent can be selected from the group consisting of a nanoparticle, a nanotube, a nutrient, an enzyme, a detergent, and a microorganism.

The invention further provides an article coated with or surface-modified with any of the described polymers.

The article can comprise a nanostructure which can be a nanoparticle or a nanotube. The nanoparticle can comprise iron. The nanotube can comprise carbon.

The article can comprise paper.

The invention further provides a detergent comprising any of the described copolymers.

The invention further provides a paper coating comprising any of the described copolymers.

The invention further provides an ink comprising any of the described copolymers.

The present invention is illustrated by the following examples. It is to be understood that the particular examples, materials, amounts, and procedures are to be interpreted broadly in accordance with the scope and spirit of the invention as set forth herein.

EXAMPLES Example 1 Sedimentation Study

Synthesis of 2-(Vinyloxy)ethyl Soyate (VOES) Monomer

VOES was synthesized as follows: First, 0.42 g of KOH was dried an oven at 140° C. for 30 minutes to remove moisture. Then, 15 g of soybean oil, 15 g of ethylene glycol monovinyl ether, and the dried KOH were mixed together in a two-neck round bottom flask and stirred for 3 hr at 70° C. The reaction mixture was then cooled to room temperature and transferred to a 250 ml separatory funnel. 100 ml of n-hexane was added to the separatory funnel and the solution washed with acidic, deionized (DI) water (pH 3-3.5) twice and then washed multiple time with DI water and finally with brine solution. The organic layer was dried over MgSO₄ and the product isolated by vacuum stripping volatiles. Yield: 13 g (84%). 1H NMR (400 MHz, CDCl₃, TMS): δ (ppm) 6.45 (m, 1H), 5.34 (m, 1.5H), 4.28 (t, 2H), 4.16 (dd, 1H), 4.01 (dd, 1H), 3.85 (t, 2H, ═CH—O—CH₂—CH₂—), 2.76 (m, 1.5H), 2.30 (t, 2H), 2.03 (m, 4H), 1.57 (m, 2H), 1.29 (m, 18H), 0.86-0.97 (m, 3H). IR (neat, cm-1): 3008 (v_(═C—H)), 2925, 2854 (v_(CH2,CH3)), 1740 (v_(C═C)), 1612 (v_(C═C)), 1117 (v_(C—O)).

Synthesis of the Tosylate of Diethylene Glycol Monoethyl Ether (Ts-DEGMEE)

In a 200 mL beaker, 8 g of NaOH was dissolved in a mixture of 40 mL of water and 30 mL of tetrahydrofuran (THF). In a 500 ml round-bottom flask equipped with a magnetic stir bar, 16.5 g of diethylene glycol monoethyl ether (DEGMEE) was dissolved in 30 mL of THF. The NaOH solution was added to the DEGMEE solution and the flask placed in ice-bath with magnetic stirring. The mixture was stirred until the temperature reached 0° C. To this mixture, a solution of p-toluenesulfonyl chloride (25.7 g) in THF (50 mL) was added dropwise with continuous stirring. Once the addition was finished, the reaction mixture was further stirred for 2 hours. The reaction mixture was then transferred to a separatory funnel and 100 ml of ice water added to the funnel. After vigorous shaking, the product was extracted three times with 100 mL of methylene chloride. The organic layer was washed with 150 mL of DI water and then twice with 150 mL of brine solution. The organic layer was then dried over MgSO₄. The colorless product was isolated by vacuum stripping volatiles. Yield: 98%. 1H NMR (400 MHz, CDCl₃, TMS): δ (ppm) 7.75 (d, 2H), 7.32 (d, 2H), 4.15 (m, 2H), 3.75-3.42 (m, 8H), 2.42 (s, 3H) 1.18 (t, 3H). IR (neat, cm-1): 2974 (v_(═C—H)), 2923, 2874 (v_(CH2,CH3)), 1619 (v_(C═C)), 1112 (v_(C—O)).

Synthesis of Triethylene Glycol Ethyl Vinyl Ether (TEGEVE) Monomer

In a three-neck, round-bottom flask equipped with a stirring magnet and nitrogen purge, 1.5 g of NaH was dissolved in 75 mL of THF and placed in an ice bath. Ethylene glycol monovinyl ether (4.7 g)/THF (30 mL) was added dropwise to the flask with continuous stirring. Once the addition was complete, the reaction mixture was stirred for another hour. The reaction mixture was then warmed to room temperature and further equipped with a condenser. A Ts-DEGMEE (15 g)/THF (45 mL) mixture was then added dropwise and the reaction temperature increased to 60° C. The reaction was continued for 20 hours before cooling to room temperature. Next, 150 mL of diethyl ether and 100 mL of THF were added and the precipitate filtered off. Volatiles were subsequently removed by vacuum stripping and the remaining material dissolved in 100 mL of methylene chloride. This solution was transferred to a separatory funnel and washed with DI water twice before drying with MgSO₄. After filtration of MgSO₄, methylene chloride was vacuum stripped to isolate the product. Yield: 85%. 1H NMR (400 MHz, CDCl₃, TMS): δ (ppm) 6.45 (m, 1H), 4.14 (dd, 1H), 3.93 (dd, 1H), 3.85-3.35 (m, 14H), 1.18 (t, 3H). IR (neat, cm-1): 2974 (v_(═C—H)), 2923, 2874 (v_(CH2,CH3)), 1596 (v_(C═C)), 1114 (v_(C—O)).

Copolymers of VOES and TEGEVE

Six different copolymers of VOES and TEGEVE were synthesized using carbocationic polymerization. A representative procedure is as follows: First, VOES and TEGEVE were dried with MgSO₄ inside a glove box to remove moisture. Glassware dried at 200° C. was used to run the reaction. The dry VOES and TEGEVE were copolymerized at 0° C. in a three-neck, round-bottom flask. The procedure used to synthesize copolymer 1 (Table 1) is as follows: 75.56 g of VOES, 8.0 g of TEGEVE, and 9.6 mg of initiator (1-isobutoxyethyl acetate (IBEA)) were dissolved in 522 mL of dry toluene and chilled to 0° C. The polymerization was initiated by the addition of 6.98 mL of the coinitiator, ethylaluminum sesquichloride solution (25 wt % in toluene) ([M]₀:[Et₃Al₂Cl₃]₀=200:10). The polymerization was terminated after 18 hours by the addition of 522 mL of chilled methanol. Table I lists the composition of the reaction mixtures used to produce the six copolymers. The addition of the methanol for terminating the polymerizations resulted in polymer precipitation for copolymers 1-4. Each of these copolymers were isolated and washed four times with methanol. The purified polymers were collected as viscous liquids after drying under vacuum (5-7 mm of Hg) overnight. For copolymers 5 and 6, after termination, methanol was removed and the polymers purified using column chromatograpy and neutral silica gel as the stationary phase to remove unreacted VOES monomer using 90/10 v/v n-hexane/ethyl acetate as the mobile phase. Once the unreacted monomer was removed, the copolymer was eluted from the column with dichloromethane. Volatiles from the solution containing the purified polymer were removed by vacuum stripping. The composition of the copolymers produced was determined using proton nuclear magnetic resonance spectroscopy (¹H NMR) and the results are displayed in Table II. Using differential scanning calorimetry (DSC), the thermal properties obtained for the copolymers were determined. Each copolymer displayed a single glass transition temperature (Tg) and copolymers 1 and 2 displayed a weak melting endotherm. Copolymers 3, 4, and 5 did not display a distinct melting transition. The Tg and melting temperatures obtained are provided in Table II. For comparison purposes, data for a polyVOES homopolymer and a polyTEGEVE homopolymer produced using carbocationic polymerization are also provided in the table. The molecular weight and molecular weight distribution (MWD) of the copolymers were characterized using gel permeation chromatography. The number-average molecular weight (Mn) and MWD data obtained are shown in Table II. Values of Mn are expressed relative to polystyrene standards.

TABLE I Composition of the polymerization mixtures used to produce copolymers of VOES and TEGEVE. Co- VOES TEGEVE Initiator initiator Formulation (M₁) (M₂) (I) (Et_(1.5)AlCl_(1.5)) Toluene ([M₁]₀:[M₂]₀:[I]₀: wt., wt., wt., volume, volume, [Et_(1.5)AlCl_(1.5)]₀) g g mg ml ml Copolymer1 75.56 8.00 9.6 6.984 522 Copolymer2 58.33 15.00 9.0 6.576 458 Copolymer3 45.20 27.12 9.8 7.175 452 Copolymer4 6.25 15.00 3.4 2.502 132 Copolymer5 2.85 15.00 3.0 2.220 110

TABLE II Data obtained for copolymers of VOES and TEGEVE. Wt. % Wt. % Tg Tm Mn Polymer VOES TEGEVE (° C.) (° C.) (g/mole) MWD polyVOES 100 0 −102 −31 19,400 1.14 polyTEGEVE 0 100 −77 — 15900 1.51 Copolymer1 85 15 −96 −35 15,900 1.24 Copolymer2 70 30 −92 −35 14,800 1.28 Copolymer3 49 51 −82 −40 18,000 1.34 Copolymer4 25 75 −80 — 16,100 1.39 Copolymer5 16 86 −79 — 15,500 1.43

These copolymers were then reacted with 3-mercaptopropionic acid to introduce carboxylic groups into the polymer via the unsaturated fatty acid ester groups derived from VOES repeat units. A general procedure for the thiol-ene reaction is as follows: copolymer, 3-mercaptopropionic acid (3 molar equivalents relative to the molar equivalents of double bonds in the copolymer), and benzophenone (0.002 molar equivalents relative to copolymer double bonds) were taken in a 50 ml beaker. The reaction was run for 5 hours using an overhead UV lamp (DYMAX 2000-EC UV flood lamp, 40-50 mW/cm²) and stirring at 500 rpm. The reaction was successfully conducted in a beaker covered with a quartz lid. Table III shows the compositions of the reaction mixtures used to produce carboxylic acid-functional copolymers. To purify the copolymers, the reaction mixtures were slowly precipitated into rapidly stirring hexane. Then, the majority of the hexane was decanted off and the remaining material dissolved in a minimum amount of THF. The THF solution was precipitated into hexane, the hexane decanted off, and the precipitate redissolved in THF. This process was done 10 times to ensure high purity of the carboxylic acid-functional copolymers. After purification, the copolymer samples were isolated by vacuum stripping the volatiles. NMR was to confirm the successful grafting of carboxylic acid groups to the copolymers and to determine the purity of the final product.

TABLE III Composition of the reaction mixtures used to produce carboxylic acid-functional copolymers from copolymers 1-5. Carboxylic acid-functional copolymers are identified by placing the letter “C” after the designation used to identify the parent copolymer. For example, “copolymer1-C” is the carboxylic acid-functional derivative produced from “copolymer1.” Formulation Copolymer Mercaptopropionic Benxophenone ([M₁]₀:[M₂]₀:[I]₀: (M1) wt., g acid (M₂) wt., g wt., mg Copolymer1-C 4.98 5.78 7 Copolymer2-C 5.07 4.84 5 Copolymer3-C 5.33 3.56 4 Copolymer4-C 5.12 1.75 2 Copolymer5-C 5.08 1.12 1 Synthesis of Zerovalent Iron Nanoparticles (NZVI)

A NaBH₄ reduction method was used to synthesize NZVIs from iron sulfate. An overhead mechanical stirrer was used for this synthesize process. 10 g of FeSO₄.7H₂O was dissolved in 100 mL of deoxygenated DI water/MeOH (70:30 v/v) mixture in a 500 mL beaker. Once the iron sulfate was dissolved, 5N NaOH solution was added dropwise to make the pH of the above solution in the range of 6.1-6.3. 50 mL of NaBH4 solution (2 M) was added with the help of a burette at a speed 0.5 mL/s. The reaction mixture was stirred for another 30 minutes after the addition was finished. Then, the nanoparticles were washed with methanol 5 times. The NZVIs were then dried in a vacuum oven overnight. After drying, the nanoparticles were left at ambient conditions for 12 hours before transferring them to a glove box. Once in the glove box, the material was ground with a mortar and pestle and stored inside a glass vial.

Polymer Coated Zerovalent Iron Nanoparticle (CNZVI) Preparation

10 mg of NZVI particles were mixed with 12 mL of an aqueous dispersion of copolymer in a 20 ml vial. Various concentrations (5 gL⁻¹, 10 gL⁻¹ and 15 gL⁻¹) of copolymer in deoxygenated DI water were used. After adding the NZVIs to the aqueous copolymer dispersions, the mixtures were sonicated for 30 minutes to break-up NZVI agglomerates and rotated in a custom-made, end-over-end shaker (85 rpm) for 72 hours to allow the copolymer to adsorb (i.e. coat) onto NZVI surfaces.

Particle Sedimentation Studies

UV-Vis spectroscopy was used to characterize the ability of the copolymers to suspend the NZVIs in deoxygenated DI water. For the measurements, a well-mixed suspension of CNZVIs (2 ml of a 1 g/L suspension of CNZVIs in water) was deposited into a quartz cuvette and the change in transmitted light intensity at a wave length of 508 nm monitored over time (2 h) using a UV spectrophotometer (Cary 50000, Varian, Calif., USA). The same evaluation was done for a control consisting of uncoated (bare) NZVI in deoxygenated DI water. FIG. 1 shows that all CNZIs exhibited lower segmentation rates than the bare NZVI. PolyVOES, copolymer1, and copolymer1-C failed to coat the NZVI because of their very poor solubility/dispersability in water, and, as a result, the sedimentation behavior of coated NZVIs involving these polymers was not performed. PolyTEGEVE coated NZVls and bare NZVIs were taken as controls. The data obtained indicate that the carboxylic acid-functional copolymers (copolymer2-C to 5-C) provide better resistance to sedimentation than their carboxylic acid-free copolymer analogs. As an example, the sedimentation behavior of copolymer5-C and copolymer5 are shown in FIG. 2, which shows that the use of copolymer5-C provides a major enhancement in the resistance to particle sedimentation. Visual analysis was also carried out to characterize particle sedimentation behavior. FIG. 3 displays images of dispersions of bare NZVIs in deoxygenated DI water and CNZVIs treated with copolymer5-C in deoxygenated DI water at different times after shaking. Since the particles are black, it can be easily seen that the CNZVIs stay suspended in water for a much longer time than the bare (i.e. uncoated) NZVIs.

Dispersion of Multiwall Carbon Nanotubes (MCNTs)

The ability of the copolymers to disperse/suspend MCNTs in water was investigated. In an 8 mL glass vial, 6 mL DI water and 60 mg of copolymer5-C were mixed well using a vortex mixer. To this mixture, 60 mg of MCNT were added and the mixture sonicated for 4 seconds. For comparison, an analogous mixture was prepared without copolymer5-C. As shown in FIG. 4, the MCNTs treated with copolymer5-C remained nicely dispersed and suspended in water two hours after preparation while the control produced without copolymer5-C showed significant settlement and agglomeration of the MCNTs.

Biodegradability of the Copolymers

The biodegradability of the copolymers was characterized using respirometric experiments and plate counts. The experimental methods utilized were as follows:

Respirometric Experiments

For respirometric experiments, BOD Trac (Hach®) was used to measure the consumption of oxygen by bacteria during the microbial metabolic processes under different conditions. Automated data transfer software was used to collect the data from the instrument. Data from the instrument were recorded as biological oxygen demand (BOD) values, and, based on these data, polymer biodegradation was assessed. The BOD experiment was carried out over a period of 21 days. Activated sludge (MLSS) from a local municipal wastewater treatment plant (Moorhead Waste Water Treatment Plant, MN) was used as the seed for microorganisms. Biodegradation was evaluated by placing 300 mg of polymer in the reactor along with BOD nutrient solution supplied by Hach® Company. Only the seed was used (in BOD nutrient solution) as the control for the experiment. Another set of controls were run with only the polymer in BOD nutrient solution (without seed). BOD nutrient was mixed with DI water and purged with oxygen for 6 h to prepare the BOD nutrient solution. The amounts of polymer, nutrient solution, and seed used in the 500 mL BOD bottles (reactors) were 300 mg of polymer, 158 mL of BOD nutrient, and 2 mL of MLSS.

Plate Count for Bacterial Growth

The plate count method was used to measure the number of viable cells in the reactors. A sterile environment was maintained during the experiment. To conduct the experiment, reactors were run as described in the previous section (respirometric experiments), but the bottles were closed with a rubber septum rather than connecting them to the respirometer. Samples were taken out with a 6 inch long sterile steel needle fitted to a sterile syringe. Nutrient agar as the growth media and serial dilution (10⁻¹ to 10⁻⁶) was done as per standard.

Results and Discussion

The data obtained from the respirometric experiments are plotted as BOD values with respect to time (FIG. 5). The results show that all three samples (i.e., soybean oil, VOES-TEGEVE copolymer (50/50 wt./wt. VOES/TEGEVE) and VOES-TEGEVE copolymer (50/50 wt./wt. VOES/TEGEVE) coated NZVI) have high BOD values compared to the controls indicating that the bacteria used the polymer as a nutrient source during their metabolic process. The data from the plate count experiments (FIG. 6) also support the result from the respirometric experiments. Results shows that VOES-TEGEVE coated NZVI had the highest number of bacteria colonies in 21 days. Based on these data, it can be concluded that the VOES-TEGEVE copolymer is biodegradable and, moreover, NZVI particles help the biodegradation process.

Example 2 Anhydride-Functional Terpolymer

Synthesis of the Tosylate of Triethylene Glycol Methyl Ether (Ts-TEGME)

In a 200 mL beaker, 8 g of NaOH was dissolved in a mixture of 40 mL water and 30 mL THF. In a 500 ml round-bottom flask, 16.5 g of triethylene glycol methyl ether (TEGME) was a dissolved in 30 mL of THF. The flask containing the mixture was placed into an ice bath and, once the temperature had reached 0° C., the NaOH solution was added to the flask. After 30 minutes, a solution of 25.7 g of p-toluenesulfonyl chloride dissolved in 70 mL of THF was added dropwise using an addition funnel. Once the addition was finished, the reaction mixture was stirred for 2 hr at 0° C. The reaction mixture was then transferred to a separatory funnel and 100 ml of ice water added. The product was extracted using 100 mL of CH₂Cl₂ twice. The organic layers were combined and then washed twice with 150 mL of DI water and then with 150 mL of brine solution. The reaction mixture was dried with MgSO₄ and the product was collected by rotary evaporation of solvent. 1H NMR (400 MHz, CDCl₃, TMS): δ (ppm) 7.75 (d, 2H), 7.32 (d, 2H), 4.2 (m, 2H), 3.7-3.4 (m, 10H), 2.4 (s, 3H) 1.2 (t, 3H). IR (neat, cm-1): 2974 (v=C—H), 2923, 2874 (vCH2,CH3), 1619 (vC═C), 1112 (vC—O).

Synthesis of Pentaethylene Glycol Methyl Vinyl Ether (PEGMVE)

In a three-neck, round-bottom flask, 1.5 g of NaH was dissolved in 75 mL of THF and the flask placed in an ice bath. Next, a solution of 4.7 g of diethylene glycol monovinyl ether in 30 mL of THF was added dropwise using an addition funnel and continuous magnetic stirring. Once the addition was finished, the reaction mixture was stirred for another one hour until the evolution of H₂ gas was no longer observed. The reaction mixture was then brought to room temperature and a condenser attached to the flask. A solution of 15 g of Ts-TEGME in 45 mL of THF was then added dropwise and the reaction temperature increased to 60° C. The reaction was continued for 20 hr before cooling to room temperature. 150 mL of diethyl ether and 100 mL of THF was then added to the mixture and the precipitate filtered off. Volatiles were removed by vacuum stripping and the remaining product dissolved in 100 mL of CH₂Cl₂. This solution was transferred to a separatory funnel and washed with DI water twice before drying with MgSO₄. The product was isolated by stripping off volatiles using a rotary evaporator. Yield: 85%. 1H NMR (400 MHz, CDCl₃, TMS): δ (ppm) 6.45 (m, 1H), 4.15 (dd, 1H), 3.95 (dd, 1H), 3.85-3.35 (m, 20H), 1.18 (t, 3H). IR (neat, cm-1): 2974 (v=C—H), 2923, 2874 (vCH2,CH3), 1596 (vC═C), 1114 (vC—O).

Synthesis of Poly(2-VOES-MA-PEGMVE)

In a 100 mL round bottom flask, 5 g of 2-VOES, 2.8 g of maleic anhydride, and 4 g of PEGMVE monomer were dissolved in 50 mL of toluene. The solution was purged with nitrogen for 15 minutes and then 80 mg of initiator [2, 2′-azobis(2-methylpropionitrile)] was added. The flask was then equipped with a condenser and placed in a silicon oil bath. The reaction was run for 16 h at 80° C. After 16 h, the reaction mixture was cooled to room temperature and methanol was added to precipitate the polymer. The precipitate was thoroughly washed with methanol and the polymer isolated by vacuum stripping volatiles. Yield: 85%. ¹H NMR (□, ppm): 5.3 (bs, 3H), 4.15 (bs, 3H), 3.9-3.2 (m, 22H), 2.7 (m, 1.3H), 2.3 (b, 2.5H), 2.0 (m, 3.5H), 1.5 (bs, 2H), 1.29-1.24 (m, 20H), 1.0-0.8 (bs, 3.7H). GPC result: Mn (relative to polystyrene standards)=24,000 g/mole, PDI=1.8.

The complete disclosure of all patents, patent applications, and publications, and electronically available material (including, for instance, nucleotide sequence submissions in, e.g., GenBank and RefSeq, and amino acid sequence submissions in, e.g., SwissProt, PIR, PRF, PDB, and translations from annotated coding regions in GenBank and RefSeq) cited herein are incorporated by reference. In the event that any inconsistency exists between the disclosure of the present application and the disclosure(s) of any document incorporated herein by reference, the disclosure of the present application shall govern. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims.

All headings are for the convenience of the reader and should not be used to limit the meaning of the text that follows the heading, unless so specified. 

What is claimed is:
 1. A copolymer comprising: at least one first monomer comprising a plant-derived vinyl ether monomer having the structure

wherein R¹ is a divalent organic group; Z is a heteroatom selected from O, N or S; R² comprises an aliphatic group obtained from a plant; and R⁶, R⁷, and R⁸ are each independently H or alkyl; at least one second monomer comprising a polyethylene glycol alkyl vinyl ether having the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20; and at least one chelating or coordinating group selected from the group consisting of carboxyl, phosphonate, phosphonic acid, sulfonate, sulfonic acid, anhydride, silane, amine, thiol, and substituted phenol, wherein the chelating or coordinating group is directly attached to the polymer backbone.
 2. The copolymer of claim 1 wherein the first monomer is obtained from a plant oil.
 3. The copolymer of claim 2 wherein the plant oil-derived monomer comprises a plurality of monomers, and wherein for each of the plurality of monomers, R² is independently a C8-C21 aliphatic group obtained from a plant oil.
 4. The copolymer of claim 1 wherein the aliphatic group is substituted with at least one functional group selected from the group consisting of an epoxide group, an acrylate-functional group, a vinyl group, and an alcohol group.
 5. The copolymer of claim 1 comprising a repeating structure comprising:

wherein x and y are independently 2 to
 500. 6. The copolymer of claim 1 further comprising at least one third monomer comprising a disubstituted double bond in which at least one substituent at each carbon of the double bond comprises a carbonyl group.
 7. The copolymer of claim 1 further comprising at least one third monomer comprising maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid.
 8. A composition comprising the copolymer of claim
 1. 9. The composition of claim 8, selected from the group comprising a detergent, a coating and an ink.
 10. The composition of claim 8 further comprising a bioremediation agent.
 11. The composition of claim 10 wherein the bioremediation agent is selected from the group consisting of a nanoparticle, a nanotube, a nutrient, an enzyme, a detergent, and a microorganism.
 12. An article coated with or surface-modified with a copolymer of claim
 1. 13. The article of claim 12 comprising a nanostructure.
 14. The article of claim 13 wherein the nanostructure comprises a nanoparticle or a nanotube.
 15. The article of claim 14 wherein the nanoparticle comprises iron.
 16. The article of claim 14 wherein the nanotube comprises carbon.
 17. The article of claim 12 comprising paper.
 18. The copolymer of claim 1, wherein the chelating or coordinating group is capable of chelating or coordinating to a metal ion or atom.
 19. The copolymer of claim 18, wherein the metal ion or atom comprises iron, zinc, magnesium, palladium or nickel.
 20. A copolymer comprising: at least one first monomer comprising a plant-derived vinyl ether monomer having the structure

wherein R¹ is a divalent organic group; Z is a heteroatom selected from O, N or S; R² comprises an aliphatic group obtained from a plant; and R⁶, R⁷, and R⁸ are each independently H or alkyl; at least one second monomer comprising a polyethylene glycol alkyl vinyl ether having the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20; at least one third monomer comprising a disubstituted double bond in which at least one substituent at each carbon of the double bond comprises a carbonyl group; and at least one chelating or coordinating group selected from the group consisting of carboxyl, phosphonate, phosphonic acid, sulfonate, sulfonic acid, anhydride, silane, amine, thiol, and substituted phenol.
 21. The copolymer of claim 20 wherein the third monomer comprises maleic anhydride, citraconic anhydride, maleic acid, itaconic acid, citraconic acid, or fumaric acid.
 22. The copolymer of claim 20 wherein the plant-derived monomer comprises a plurality of plant oil-derived monomers, and wherein for each of the plurality of monomers, R² is independently a C8-C21 aliphatic group obtained from a plant oil.
 23. The copolymer of claim 20 wherein the aliphatic group is substituted with at least one functional group selected from the group consisting of an epoxide group, an acrylate-functional group, a vinyl group, and an alcohol group.
 24. The copolymer of claim 20 wherein the aliphatic group is substituted with the chelating or coordinating group.
 25. The copolymer of claim 20 comprising a repeating structure

wherein x and y are independently 2 to
 500. 26. The copolymer of claim 20, wherein the chelating or coordinating group is capable of chelating or coordinating to a metal ion or atom.
 27. The copolymer of claim 26, wherein the metal ion or atom comprises iron, zinc, magnesium, palladium or nickel.
 28. A composition comprising the copolymer of claim
 20. 29. The composition of claim 28, selected from the group comprising a detergent, a coating and an ink.
 30. The composition of claim 28 further comprising a bioremediation agent.
 31. The composition of claim 30 wherein the bioremediation agent is selected from the group consisting of a nanoparticle, a nanotube, a nutrient, an enzyme, a detergent, and a microorganism.
 32. An article coated with or surface-modified with a copolymer of claim
 20. 33. The article of claim 32 comprising a nanostructure.
 34. The article of claim 33 wherein the nanostructure comprises a nanoparticle or a nanotube.
 35. The article of claim 34 wherein the nanoparticle comprises iron.
 36. The article of claim 34 wherein the nanotube comprises carbon.
 37. The article of claim 32 comprising paper.
 38. A copolymer comprising: at least one first monomer comprising a plant-derived vinyl ether monomer having the structure

wherein R¹ is a divalent organic group; Z is a heteroatom selected from O, N or S; R² comprises an aliphatic group obtained from a plant; and R⁶, R⁷, and R⁸ are each independently H or alkyl; at least one second monomer comprising a polyethylene glycol alkyl vinyl ether having the structure

wherein R¹² is divalent organic group that functions as a spacer between the vinyl ether and the second ether functionality; R¹³ is a monovalent alkyl; R⁹, R¹⁰, and R¹¹ are each independently H or alkyl; and n is 2 to 20; and at least one chelating or coordinating group selected from the group consisting of a carboxylated thiol, an alkoxysilane group, or —N(CH₂CO₂H)₂.
 39. The copolymer of claim 38, comprising a repeating structure comprising:

wherein x and y are independently 2 to
 500. 40. The copolymer of claim 38, wherein the chelating or coordinating group is capable of chelating or coordinating to a metal ion or atom.
 41. The copolymer of claim 40, wherein the metal ion or atom comprises iron, zinc, magnesium, palladium or nickel.
 42. A composition comprising the copolymer of claim
 38. 43. The composition of claim 42, selected from the group comprising a detergent, a coating and an ink.
 44. The composition of claim 42 further comprising a bioremediation agent.
 45. The composition of claim 44 wherein the bioremediation agent is selected from the group consisting of a nanoparticle, a nanotube, a nutrient, an enzyme, a detergent, and a microorganism.
 46. An article coated with or surface-modified with a copolymer of claim
 38. 47. The article of claim 46 comprising a nanostructure.
 48. The article of claim 47 wherein the nanostructure comprises a nanoparticle or a nanotube.
 49. The article of claim 48 wherein the nanoparticle comprises iron.
 50. The article of claim 48 wherein the nanotube comprises carbon.
 51. The article of claim 46 comprising paper. 